Diisocyanato tricyclodecane



United States Patent No. 799,409, now Patent No. 3,069,468, dated Dec.18,

1962. Divided and this application Sept. 10, 1962, Ser. No. 222,88

1 Claim. (Cl. 250-453) This invention relates to certain noveltricyclodecanes and to a process for their preparation. Moreparticularly, the present invention relates to3,10-diaminotricyclo[5.2.l.0 ]decane and its functional derivative,3,10- diisocyanatotricyclo[5.2.1.0 ]decane.

The novel materials of the present invention may be represented by thefollowing general formula:

monomer in the production of nonyellowing polyurethane resins.

3,IO-diaminotricyclo[5.2.1.0 ]decane can be prepared by thehydrogenation of l,8-dioximino-4,7-methano-3a,

genation is a known compound which can be prepared from cyclopentadiene,nitrosyl chloride, and sodium eth oxide by the methods described inco-pending application, Serial No. 783,701, now Patent No. 3,068,287.

The hydrogenation reaction should be conducted in the presence of from 1to 250 mols, per mole of dioxime, of anhydrous ammonia and preferably isconducted using from about 5 to about 50 mols of anhydrous ammonia permole of dioxime. The hydrogenation may be con- 1 ducted at a temperatureof from about 0 to about 250 C. but is preferably conducted at atemperature of from about to 200 C. and at a pressure of from about 100to 4000 p.s.i.g., preferably from about 1000 to about 2000 p.s.i.g. Ahydrogenation catalyst should preferably be employed. Suitablehydrogenation catalysts include Raney nickel, cobalt, platinum,palladium, arid the like. The catalyst should be present in an amountcorresponding to from about 5 to about 100 parts by Weight per 100 partsby weight of dioxime. While not essential to the reaction, an inertsolvent, such as methanol, p-dioxane, ethanol, or diethylene glycoldiethyl ether may be employed in an amount corresponding to from about 2to about 50 parts by weight per part of dioxime.

3,l0-diisocyanatotricyclo[S.2.l.0 ]decane can be prepared by reacting3,IO-diaminotricyclo[5.2.1.0 ]decane with phosgene. The phosgene shouldbe employed in an amount corresponding to from about 2 to 200 mols permol of the decane. The reaction should be conducted at a temperature offrom about to about 350 C., preferably from about to about 300 C. andshould be conducted in the presence of inert solvents such as benzene,toluene, chlorobenzene, dichlorobenzene, trichlorobeniene, chlorinatedtoluene, chlorinated Xylenes, chlorinated naphthalenes, sulfolanes, andtetrahydronaphthalene.

The following example is illustrative of the preparation j of thedioxirnino compound employed in the present 4,7,7a-tetrhydroindene. Theindene used in the hydr0- invention.

Example] (1.) ZC H OH 'l't Zita. ZG H ONa i H ethanol sodium sodiumethoxide (zyc u oua N001 c u ouo NaCl sodium nitrosyl ethyl sodiumethoxide chloridenitrite chloride (3) U c a ouo c n oNa -----9 1| zc aoa cyclopencaethyl sodium diene nitrite ethoxide NONa ethanol.

' sodium salt of oximinocyclopenta die'ne non I NONa II NOH l ZNaHCOcarbon 1, 8-dioximino-4, 7 sodium dioxide methane-3a 7 7a-=bicartetrahydroindene bonaee Anhydrous ethanol (3000 ml.) was stirredand refluxed, while 69 grams of sodium metal (3 mols) were dissolved.The resulting solution of sodium ethoxide was stirred at .10 to 15 C.While 94 grams of nitrosyl chloride (72 ml. at 30 C., 1.56 mols) werefed over a period of 20 minutes. The mixture was stirred at 2 to 7 C.while 94.5 grams of freshly distilled cyclopentadiene (1.43 mols) werefed over a period of 2 hours. After a reaction period of 2 hours at 7 to22 C., the reaction mixture was added to 1500 ml. of cold water (5 C.)and stripped to a kettle temperature of 25 C. at mm. to remove ethanol.The residue was extracted several times with ethyl ether to removebase-insoluble impurities. The basic aqueous solution (pH 12) Wassaturated with carbon dioxide at 8 C. to reduce the pH to 7.8 andprecipitate the crude dioxime. Both the precipitate and the aqueouslayer were extracted continuously with ethyl ether to separate thedioxime from tarry by-products. Evaporation of the ether from theextract yielded 87.5 grams (64 percent yield) of dioxime as a light tansolid in several crops melting in the range of 155 to 162 C. Ananalytical sample was prepared by dissolving 20 grams of the dioxime in100 ml. of 2 N sodium hydroxide plus 50 ml. of water. After filtration,the solution was neutralized with carbon dioxide and extracted withethyl ether several times. The extracts were combined and the etherevaporated to obtain -17.2 grams of pure dioxime of melting point 160 to164 C. Found 63.0 percent C (theory 63.14 percent), 5.9 percent H(theory 5.3 percent), 14.3 percent N (theory 14.7 percent). The infraredabsorption spectrum supported the assigned structure.

The following examples are illustrative of the present invention.

Example 11 NOH n l, B-dioximinio-, 7-methano- 3a 4 Z 7a-tetrahydroindeneA mixture of 64.3 grams (0.338 mols) of1,8-dioximino-4,7-methano-3a,4,7,7a-tetral1ydroindene, 250 grams ofRaney nickel catalyst, and 1500 ml. of ethanol was divided equallybetween two 3-liter stainless steel rocker autoclaves. To each autoclavewas then added 689 grams of anhydrous ammonia (40.5 mols). Thus themolar ratio of ammonia to dioxime was 240/1. Each charge was thenhydrogenated at 11000 to 1600 p.s.i.g. to a maximum temperature of 90 C.The hydrogen absorption appeared to be complete after two hours at 27C., but the temperature was gradually increased to 90 C. over a periodof six hours to ensure complete hydrogenation.

for the diamine is 83, the purity was 98.6 percent. The yield was 72percent based on the dioxime. The distillation residue weighed only 4.8grams and the ratio of distilled product to residue was 8.5.

Example III A mixture of 49.7 grams (0.262 mols) of1,8-dioximino-4,7-methano-3a,4,7a-tetrahydroindene, 300 ml. of ethanol,and grams of Raney nickel catalyst was hydrogenated at 2000 to 3500p.s.i.g. and at 110 to 150 C. for 7.5 hours. The hydrogenated mixture,which contained ammonia, was filtered and distilled to obtain thefractions listed in Table I below.

TABLE I Weight, Equivalent Fraction grams Distillation Range Weight asAmine 1 5.8 tie-100 0.11 mm 96.5 2 8.0 110-125 0J2 mm 101.0 Residue 27.2 126. 7

The residue had a molecular weight of 351 by the Menzies-Wright method.The yield of 3,10-diaminotricyclo[5.2.l.0 ]-decane in this experimentwas about 16 percent based on the dioxime.

Example IV A mixture of 51.8 grams (0.273 mols) of1,8-dioximino-4,7-methano, 3a,4,7,7a-tetrahydroindene, 300 ml. ofethanol, 40 grams of Raney nickel, and 10 grams of anhydrous ammonia(.59 mols, molar ratio ammonia to dioxime of 2.2) was hydrogenated at500 p.s.i.g. while heating gradually to 100 C. over a period of 5 hours.

The filtered mixture was distilled to obtain the fractions listed belowin Table II.

The hydrogenated mixtures were combined, filtered to The yield of3,10-diaminotricyclo[5.2.1 ]-decane remove catalyst, and distilled toisolate 41 grams of 3,10- was about 43 percent based on the dioxime.

Example V H Nl-lz H CO H 2 NCO 3 10-diaminotrihesgene 3IG-diisgcyanatohydrcgen' ce1o[s. 2. 1. 0 7- siieyctois. 2.1. 0 chlzddedec ane decane diaminotricyclo[5.2.l.0 ]decane as a colorless liquidhaving these properties: boiling range 87 to 98 C./0.5 mm., 84.2equivalent weight as amine by titration with A solution of3,IO-diaminotricycloE5.2.l.0 ]decane (33.3 grams, 0.20 mol) in 300 ml.of o-dichlorobenzene was stirred at 90 to C. while carbon dioxide wasperchloric acid. Since the theoretical equivalent weight 75 bubbled infor 22 hours. The resulting slurry was cooled to O C., and 90 grams ofphosgene were added drop- Wise with stirring during one hour. Morephosgene (36 grams) was added while the slurry was allowed to warm toroom temperature. The slurry was heated to 160 C. and phosgene additioncontinued at an approximate rate of 25 grams per hour for ten hours.After purging with nitrogen and removal of solvent under reducedpressure, 39 grams of 3,10-diisocyanatotricyclo[5.2.1.0 ]decane weredistilled, boiling point 130 to 134 C./ .5 mm. The yield was 90 percentbased on the diamine.

Analysis.Calcu1ated for C H N O flC, 66.02; H, 6.47; N, 12.84. Found: C,66.10; H, 6.67; N, 12.48.

Example V1P0lyurethane Foam Prepared From 3,10- Diisocyanatotricyclo [5.2.1 .0 ]Decane Ten grams of a polyester of adipic acid and diethyleneglycol, 4.4 grams of 3,IO-diisocyanatotricyclo[5.2.1.0

decane, and 0.3 grams of emulsifier comprising a nonionic fatty amidocondensate were thoroughly mixed in a beaker. Dibutyltin acetatecatalyst (0.15 gram) was added and mixing continued until thetemperature of the mixture rose to C. Water (0.20 gram) Was then addedand rapidly stirred into the mixture. Foaming occurred after afour-minute exposure in an oven at C.

Unless otherwise indicated, as used throughout this specification, allparts and percentages are by weight.

This application is a divisional application of our copendingapplication, Serial No. 799,409, filed on March 16, 1959, now Patent No.3,069,468.

What is claimed is:

3 ,10-diisocyanatotricyclo[5.2.1.0 decane.

No references cited.

